Photo-labile pro-fragrance conjugates

ABSTRACT

The present invention relates to photo-labile pro-fragrance conjugates comprising: a) a photo-labile unit which upon exposure to electromagnetic radiation is capable of releasing a pro-fragrance unit; and b) a pro-fragrance unit, which when so released is either i) a pro-fragrance compound capable of releasing a fragrance raw material; or ii) a fragrance raw material. The present invention relates to systems for delivering fragrances to a situs, and to laundry detergent compositions, fine fragrances, personal care and hair care compositions comprising said systems.

CROSS REFERENCE TO RELATED APPLICATIONS

This application is a continuation of and claims priority under 35U.S.C. §120 to U.S. application Ser. No. 11/654,085 filed Jan. 17, 2007,which in turn is a continuation of and claims priority to U.S.application Ser. No. 11/446,649 filed Jun. 5, 2006, (now abandoned)which in turn is a continuation of and claims priority to U.S.application Ser. No. 11/148,688 filed Jun. 9, 2005, (now U.S. Pat. No.7,109,153 B2) which in turn is a divisional of and claims priority toDivisional application Ser. No. 10/693,733 filed Oct. 24, 2003, (nowU.S. Pat. No. 6,987,084 B2) which in turn is a Divisional Application ofand claims priority to application Ser. No. 10/001,029 filed Nov. 2,2001, (now abandoned), which claims priority under Title 35, UnitedStates Code 119(e) from Provisional Application Ser. No. 60/246,811,filed Nov. 8, 2000, (now abandoned).

FIELD OF THE INVENTION

The present invention relates to photo-labile pro-fragrance conjugates,which are capable of releasing a fragrance raw material in a sequence ofchemical reaction steps that include a photo-activated release of anitrogen-containing pro-fragrance compound. The conjugates are useful informulating fragrance delivery systems. The conjugates of the presentinvention are capable of delivering any type of fragrance raw material.

BACKGROUND OF THE INVENTION

Pro-fragrances and pro-accords have been used to enhance the delivery offragrance raw materials and to sustain their duration. Typicallypro-fragrances and pro-accords deliver alcohol, ketone, aldehyde, andester fragrance raw materials via substrates which are hydrolyzed by oneor more mechanisms, inter alia, the acidic pH of skin, nascent moisture.

Fragrances or odors not only provide a pleasant aesthetic benefit, butalso serve as a signal. For example, foods, which have soured or are nolonger edible, may develop smells, which are repulsive and send a signalthat they are no longer palatable. Therefore, the delivery of an aromasensory signal is also a benefit, which a pro-fragrance can provide.

However, pro-fragrances and pro-accords typically rely on the break downof a chemical species not based on accidental circumstance but ondeliberate execution. There are currently no fragrance or odor releasingcompounds which involve release of fragrances by way of a controlledchemical cascade initiated by exposure to electromagnetic radiation,inter alia, UV light. The present invention provides a means fordelivering a fragrance or an accord wherein the delivery of saidfragrance or said accord is instigated by exposure to light.

SUMMARY OF THE INVENTION

The present invention meets the aforementioned need in that it has beensurprisingly discovered that fragrance raw materials can be delivered byphoto-labile pro-fragrance conjugates. The photo-labile pro-fragranceconjugates of the present invention are activated by the exposure of theconjugates to electromagnetic radiation, which is the initial step in achemical cascade resulting in the ultimate release of a fragrance rawmaterial. One of the steps in the cascade involves photochemicallyinitiated fragmentation of a chemical bond between a photo-labile unitand a nitrogen atom contained within a pro-fragrance unit.

The conjugates of the present invention comprise:

-   -   a) a photo-labile unit which upon exposure to electromagnetic        radiation is capable of releasing a pro-fragrance unit; and    -   b) a pro-fragrance unit, which when so released is either        -   i) a pro-fragrance compound capable of releasing a fragrance            raw material; or        -   ii) a fragrance raw material.

The present invention also relates to a photo-labile fragrance conjugatedelivery system comprising:

-   -   A) from about 0.001% by weight, of a photo-labile pro-fragrance        conjugate, said conjugate comprising:        -   a) a photo-labile unit which upon exposure to            electromagnetic radiation is capable of releasing a            pro-fragrance unit;        -   b) a pro-fragrance unit, which when so released is either            -   i) a pro-fragrance compound capable of releasing a                fragrance raw material; or            -   ii) a fragrance raw material; and    -   B) the balance carriers and adjunct ingredients.

These and other objects, features, and advantages will become apparentto those of ordinary skill in the art from a reading of the followingdetailed description and the appended claims. All percentages, ratiosand proportions herein are by weight, unless otherwise specified. Alltemperatures are in degrees Celsius (° C.) unless otherwise specified.All documents cited are in relevant part, incorporated herein byreference.

DETAILED DESCRIPTION OF THE INVENTION

The present invention relates to photo-labile pro-fragrance conjugates,which are stable until activated by exposure to electromagneticradiation. The conjugates of the present invention are capable ofreleasing any type of perfume raw material, inter alia, alcohols,ketones, aldehydes, via a single- or multi-step process that isinitiated by the photo-induced fragmentation of a chemical bond betweenthe photo-labile unit and a nitrogen atom in the pro-fragrance unit.

The conjugates of the present invention can be depicted as compoundshaving a photo-labile unit and a pro-fragrance unit which are connectedto one another directly or optionally by way of a linking unit. Theconjugates can be represented by the formula:[photo-labile unit]-(L)_(n)-[pro-fragrance unit]wherein the linking unit, L, is present when the index n is equal to 1and absent when n is equal to 0.

For the purposes of the present invention the term “photo-labile unit”is defined herein as “a unit which upon exposure to electromagneticradiation becomes the photo-fragment compound by fragmenting from theparent photo-labile pro-fragrance conjugate.” In some embodiments of thepresent invention it may be advantageous that the photo-fragmentcompound does not interfere with the aesthetic quality or character ofthe released fragrance or pro-fragrance compound. In the presence oflight, the photo-labile unit serves to trigger the chemical reaction orreaction cascade that ends with the ultimate release of one or morefragrance raw materials.

For the purposes of the present invention the term “pro-fragrance unit”is defined herein as “that portion of the photo-labile pro-fragranceconjugate, which gives rise to the fragrance compound or pro-fragrancecompound as a result of exposure of the photo-labile pro-fragranceconjugate to electromagnetic radiation or “light.”

For the purpose of the present invention the term “pro-fragrancecompound” is defined herein as “a chemical species, which by undergoingone or more chemical transformations results in the release of one ormore fragrance compounds.” Fragrance compounds and fragrance rawmaterials are terms which refer to the final “perfume” ingredients whichare delivered and are used interchangeably herein. What is meant hereinby the term “chemical transformation” includes conversion to a speciesof different molecular formula by any means, inter alia, hydrolysis,photolysis, thermolysis, autoxidation, addition, elimination andsubstitution reactions, as well as conversion to a species with the samemolecular formula, but having an altered chemical orientation, i.e.,isomerized.

The chemical cascade, which begins the release of a fragrance rawmaterial, may be controlled by requiring a certain wavelength ofelectromagnetic radiation to be present to initiate the releasesequence. For example, “outside light”, which typically comprises thefull range of UV light, may be required to initiate the release of thefragrance precursor. In some cases, high temperatures may also initiatethe chemical cascade.

Photo-Labile Pro-Fragrance Conjugates

The present invention relates to conjugates, which upon exposure tovisible light or other forms of electromagnetic radiation, inter alia,UV light, releases a fragrance raw material after a series of chemicaltransformations, wherein said series involves at least two discretesteps. The photo-labile pro-fragrance conjugates of the presentinvention comprise:

-   -   a) a photo-labile unit, which upon exposure to electromagnetic        radiation is capable of releasing a pro-fragrance unit; and    -   b) a pro-fragrance unit, which when so released is either        -   i) a pro-fragrance compound capable of releasing a fragrance            raw material; or        -   ii) a fragrance raw material.

The conjugates of the present invention comprise a chemical specieshaving a photo-activated unit which is bonded to the nitrogen atom of apro-fragrance compound, a fragrance raw material, or a linking unitwhich is subsequently bonded to the nitrogen atom of a pro-fragrancecompound, or a fragrance raw material, wherein said chemical bond iscapable of being broken when said conjugate is exposed toelectromagnetic radiation.

For the purposes of the present invention the term “hydrocarbyl” isdefined herein as “any unit which comprises carbon and hydrogen atoms,whether linear, branched, cyclic, and regardless of how many of thehydrogen atoms are substituted for with a suitable “substituted” unit asdefined herein below.” Non-limiting examples of “hydrocarbyl” unitsinclude methyl, benzyl, 6-hydroxyoctanyl, m-chlorophenyl,2-(N-methylamino)propyl, and the like.

The terms “unit which can substitute for hydrogen” and “substituted” areused throughout the specification and for the purposes of the presentinvention these terms are defined as “chemical moieties which canreplace a hydrogen atom on a hydrocarbon chain, an aryl ring, and thelike, or replacement of a hydrogen atom, two hydrogen atoms, or threehydrogen atoms from a carbon atom to form a moiety, or the replacementof hydrogen atoms from adjacent carbon atoms to form a moiety.” Forexample, a substituted unit that requires a single hydrogen atomreplacement includes halogen, hydroxyl, and the like. A two-hydrogenatom replacement includes carbonyl, oximino, and the like. Threehydrogen replacements includes cyano, and the like. The term substitutedis used throughout the present specification to indicate that a moiety,inter alia, aromatic ring, alkyl chain, can have one or more of thehydrogen atoms replaced by a substituent. For example, 4-hydroxyphenylis a “substituted aromatic carbocyclic ring”, and 3-guanidinopropyl is a“substituted C₃ alkyl unit.”

The following are non-limiting examples of moieties, which can replacehydrogen atoms on carbon to form a “substituted hydrocarbyl” unit:

i) —NHCOR³⁰;

ii) —COR³⁰;

iii) —COOR³⁰;

iv) —COCH═CH₂;

v) —C(═NH)NH₂;

vi) —N(R³⁰)₂;

vii) —NHC₆H₅;

viii) ═CHC₆H₅;

ix) —CON(R³⁰)₂;

x) —CONHNH₂;

xi) —NHCN;

xii) —OCN;

xiii) —CN;

xiv) F, Cl, Br, I, and mixtures thereof;

xv) ═O;

xvi) —OR³⁰;

xvii) —NHCHO;

xviii) —OH;

xix) —NHN(R³⁰)₂;

xx) ═NR³⁰;

xxi) ═NOR³⁰;

xxii) —NHOR³⁰;

xxiii) —CNO;

xxiv) —NCS;

xxv) ═C(R³⁰)₂;

xxvi) —SO₃M;

xxvii) —OSO₃M;

xxviii) —SCN;

xxix) —P(O)H₂;

xxx) —PO₂;

xxxi) —P(O)(OH)₂;

xxxii) —SO₂NH₂;

xxxiii) —SO₂R³⁰;

xxxiv) —NO₂;

xxxv) —CF₃, —CCl₃, —CBr₃;

xxxvi) and mixtures thereof;

wherein R³⁰ is hydrogen, C₁-C₂₀ linear or branched alkyl, C₆-C₂₀ aryl,C₇-C₂₀ alkylenearyl, and mixtures thereof; M is hydrogen, or a saltforming cation. Suitable salt forming cations include, sodium, lithium,potassium, calcium, magnesium, ammonium, and the like. Non-limitingexamples of an alkylenearyl unit include benzyl, 2-phenylethyl,3-phenylpropyl, 2-phenylpropyl.

Photo-Labile Units

The photo-labile units of the present invention may be any moiety, whichis capable of instigating the release of a fragrance raw material bybreaking the chemical bond between the photo-labile unit and one ofthree components:

-   -   a) a fragrance raw material unit thereby directly releasing a        fragrance raw material;    -   b) a pro-fragrance unit thereby instigating a sequence of one or        more chemical transformations which release a fragrance raw        material; or    -   c) a linking group which further undergoes a sequence of one or        more chemical transformations which subsequently release a        fragrance raw material or pro-fragrance unit.

A first aspect of photo-labile units according to the present inventionrelate to units which are aryl acrylic acid units having the formula:

wherein R is a fragrance raw material or a unit capable of releasing afragrance raw material; each R¹ is independently hydrogen, a unit whichcan substitute for hydrogen, C₁-C₁₂ substituted or unsubstitutedhydrocarbyl unit, each R² is independently hydrogen, C₁-C₁₂ substitutedor unsubstituted hydrocarbyl unit, and mixtures thereof; X is selectedfrom the group consisting of —OH, —OC(O)R¹², —OC(O)OR¹², —NHR¹², andmixtures thereof; R¹² is H, C₁-C₁₂ substituted or unsubstituted alkyl,and mixtures thereof. These units are capable of releasing a fragranceraw material unit, a pro-fragrance unit, or a linking group bondedfragrance raw material unit or pro-fragrance unit; the photo-fragmentcompound having the formula:

which can optionally be a fragrance raw material itself, inter alia,coumarin.

Non-limiting examples of photo-labile units included in this firstaspect include a pro-fragrance wherein X is —NH₂, the R¹ unit ishydroxy, and both R² units are hydrogen which relates to3-(2-amino-4-hydroxyphenyl)-acrylamide fragrance raw materials havingthe formula:

Another example relates to photo-labile units having the formula:

wherein both R¹ and X are hydroxyl.

A second aspect of the present invention relates to a photo-labilepro-fragrance conjugates having the formula:

wherein R¹ is one or more electron donating groups; non-limitingexamples of which include hydroxy, C₁-C₁₂ linear or branched alkoxy,—N(R¹²)₂, and mixtures thereof; R¹² is H, C₁-C₁₂ alkyl, and mixturesthereof, and the like.

A third aspect of the photo-labile units relates to aryl units havingthe formula:

A fourth aspect of the photo-labile units relates to aryl units havingthe formula:

wherein B is a photo-labile unit which reactivity is enhanced ormodulated by the aryl unit which comprises the balance of thephoto-labile component. One embodiment of this aspect relates to siliconatom comprising units having the formula:

wherein R¹ is the same as defined herein above. Further non-limitingexamples of embodiments of this aspect of the photo-labile units includecompounds having the formula:

Linking Units

Depending upon the structure of the photo-labile unit and the rate atwhich the formulator desires the final fragrance raw material to bereleased, the use of an optional linking unit, L, may be desired ornecessary. An example of a compound having an L unit present has theformula:

one embodiment of which has the formula:

One aspect of the present invention relates to L units which are—OC(O)—, —NR³C(O)—, —OC(R³R⁴)—, and —C(O)— carbonyl units. However, anysuitable unit which facilitates the breakdown of the releasedpro-fragrance can serve as a linking unit in the photo-activatedpro-fragrance conjugates of the present invention.

When the pro-fragrance unit is released from the photo-labile unit whena linker unit is present, the release of the photo-fragment compound andpro-fragrance or fragrance compound is accompanied by the release of alinker compound. For example, when the L unit is —OC(O)—, the linkercompound is CO₂.

When the L unit is —OC(R³R⁴)— the linker compound released can be analdehyde or a ketone. In one aspect of the present invention, thealdehyde or ketone released is a perfume raw material.

Non-limiting examples of photo-activated compounds comprising an L unitinclude:

Pro-fragrance Units

Pro-fragrance units are released from the parent conjugate moleculeswhen the conjugate is fragmented by a photochemical reaction. Thepro-fragrance units of the present invention are attached to thephoto-labile units either directly or by way of an optional linkingunit, L.

As will be understood by the formulator, not all fragrance raw materialscan be released from the same form of pro-fragrance. The two primaryaspects of the present invention as it relates to release of apro-fragrance unit are determined by the type of reaction whichultimately releases the final fragrance raw material.

The first aspect relates to type A release which involves aretro-Michael reaction, and the second aspect relates to type B releasewhich involves a hydrolysis reaction.

Type A Release

The first aspect of the pro-fragrance unit component of the presentinvention relates to the release of fragrance raw material precursorswhich undergo a retro-Michael reaction.

Without wishing to be limited by theory, the reaction cascade whichreleases the fragrance raw material via retro-Michael reaction isbelieved to proceed according to the general scheme as depicted belowfor the release of a α,β-unsaturated ketone, inter alia, damascone.1. A First Photo-Isomerization Step:

2. A Second Pro-Fragrance Unit Elimination Step:

3. A Third Retro-Michael Elimination Step:

The pro-fragrances which comprise this aspect of the present inventionhave the formula:

wherein each R³ is independently hydrogen, substituted or unsubstitutedC₁-C₃₀ hydrocarbyl, and mixtures thereof.

One embodiment of this aspect of the present invention relates topro-fragrances having the formula:

wherein each R⁴ is independently selected from the group consisting of:

i) hydrogen;

ii) C₁-C₂₂ substituted or unsubstituted, branched or unbranched alkyl;

iii) C₂-C₂₂ substituted or unsubstituted, branched or unbranchedalkenyl;

iv) C₂-C₂₀ substituted or unsubstituted, branched or unbranchedhydroxyalkyl;

v) C₇-C₂₀ substituted or unsubstituted alkylenearyl;

vi) C₃-C₂₀ substituted or unsubstituted cycloalkyl;

vii) C₆-C₂₀ aryl;

Viii) C₅-C₂₀ heteroaryl units comprising one or more heteroatomsselected from the group consisting of nitrogen, oxygen, sulfur, andmixtures thereof;

ix) two R⁴ units can be taken together to form one or more aromatic ornon-aromatic, heterocyclic or non-heterocyclic, single rings, fusedrings, bicyclo rings, spiroannulated rings, or mixtures thereof, saidrings comprising from 3 to 20 carbon atoms and one or more heteroatomsselected from the group consisting of nitrogen, oxygen, sulfur, andmixtures thereof;

x) and mixtures thereof;

G¹ and G² are each independently hydrogen, C₁-C₂₀ linear or branchedhydrocarbyl, —Y, —C(O)Y, and mixtures thereof; Y is C₆-C₁₀ substitutedor unsubstituted cyclic alkyl. Non-limiting examples of embodiments of Yinclude 2,6,6-trimethylcyclohex-2-enyl, 2,6,6-trimethylcyclohex-1-enyl,2,6,6-trimethylcyclohex-1-enyl, 2,6,6-trimethylcyclohex-3-enyl, and thelike.

Another embodiment of this aspect of the present invention relates topro-fragrances having the formula:

wherein G¹ and G² are each independently —CH₃, —C(O)CH₃, —Y, —C(O)Y, andmixtures thereof; Y is selected from the group consisting of:

i) 2,6,6-trimethylcyclohex-2-enyl having the formula:

ii) 2,6,6-trimethylcyclohex-1-enyl having the formula:

iii) 2,6,6-trimethylcyclohex-1-enyl having the formula:

iv) 2,6,6-trimethylcyclohex-3-enyl having the formula:

v) and mixtures thereof.

The following is a non-limiting example of a photo-labile pro-fragrancewhich releases a fragrance raw material (6-damascone) via retro-Michaelelimination.

The following is a non-limiting example of a photo-labile pro-fragrancewhich comprises a linking unit and which releases a fragrance rawmaterial (δ-damascone) via retro-Michael reaction.

However, R³ units in another aspect of the present invention can betaken together with an R¹ or R² unit of the photo-labile unit or with anL unit to form a C₂-C₆ heterocyclic ring for example, the conjugatehaving the formula:

which is capable of releasing damascone and a photo-fragment compoundhaving the proposed formula:Type B Release

The second aspect of the pro-fragrance unit component of the presentinvention relates to the release of fragrance raw material precursorswhich undergo a hydrolysis step in the cascade releasing the fragranceraw material.

Without wishing to be limited by theory, the reaction cascade whichreleases the fragrance raw material via hydrolysis reaction is believedto proceed according to the general scheme as depicted below for therelease of an aldehyde, inter alia, citral.1. A First Photo-Isomerization Step:

2. A Second Pro-Fragrance Unit Elimination Step:

3. A Third Hydrolysis Step:

However, the above scheme only illustrates the general case ofpro-fragrances which are in the form of oxazolidinones or oxazineshaving the formula:

each of which is capable of releasing an aldehyde having the formulaR⁵CHO.

However, the heterocyclic ring embodiment which comprises thepro-fragrance units of the present invention which have the generalformula:

wherein Z is oxygen or sulfur; in one embodiment comprisingoxazolidines, Y is oxygen and the index m is 1.

R⁵ and R⁶ units are selected such that upon hydrolysis of thepro-fragrance compound, aldehyde or ketone fragrance raw materials arereleased. When an aldehyde is released R⁶ is hydrogen.

As stated herein above, R⁵ units can be any substituted or unsubstitutedhydrocarbyl unit, non-limiting examples of which include R⁵ units whichcomprise:

-   -   a) C₆-C₂₂ substituted or unsubstituted linear alkyl; C₆-C₁₂        alkyl when aliphatic aldehydes are released, inter alia,        hexanal, octanal, nonanal, decanal, undecanal, and dodecanal;    -   b) C₆-C₂₂ substituted or unsubstituted branched alkyl;        2-methyldecanal, 2-methylundecanal;    -   c) C₆-C₂₂ substituted or unsubstituted linear alkenyl; C₆-C₁₂        alkenyl when unsaturated linear aldehydes are released, inter        alia, trans-4-hexenal, cis-4-heptenal, and 10-undecenal;    -   d) C₆-C₂₂ substituted or unsubstituted branched alkenyl; C₉ or        C₁₄ branched alkyl when the released aldehyde is a terpene or        sesquiterpene aldehyde, inter alia, citronellal, citral;    -   e) C₆-C₂₂ substituted or unsubstituted cycloalkyl; C₉ or C₁₁        alkyl substituted cycloalkyl when the released ketone is cyclic        terpenoid, inter alia, α, β, γ, and δ ionone or damascone;    -   f) C₆-C₂₂ substituted or unsubstituted branched cycloalkyl;    -   g) C₆-C₂₂ substituted or unsubstituted cycloalkenyl;    -   h) C₆-C₂₂ substituted or unsubstituted branched cycloalkenyl;    -   i) C₆-C₂₂ substituted or unsubstituted aryl;    -   j) C₆-C₂₂ substituted or unsubstituted heterocyclicalkyl;    -   k) C₆-C₂₂ substituted or unsubstituted heterocyclicalkenyl;    -   l) and mixtures thereof;    -   R⁶ units comprise:    -   a) hydrogen;    -   b) C₁-C₁₀ substituted or unsubstituted linear alkyl; as in the        case of methyl ketones, inter alia, α, β, γ, and δ ionone;    -   c) C₃-C₁₀ substituted or unsubstituted branched alkyl; for        example, tagetone wherein R is 2-methyl-1,3-dieneyl and R¹ is        isobutyl;    -   d) C₂-C₁₀ substituted or unsubstituted linear alkenyl; as in the        case of α, β, γ, and δ damascone;    -   e) C₃-C₁₀ substituted or unsubstituted branched alkenyl;    -   f) C₃-C₁₅ substituted or unsubstituted cycloalkyl;    -   g) C₄-C₁₅ substituted or unsubstituted branched cycloalkyl;    -   h) C₄-C₁₅ substituted or unsubstituted cycloalkenyl;    -   i) C₅-C₁₅ substituted or unsubstituted branched cycloalkenyl;    -   j) C₆-C₁₅ substituted or unsubstituted aryl;    -   k) C₆-C₂₂ substituted or unsubstituted heterocyclicalkyl;    -   l) C₆-C₂₂ substituted or unsubstituted heterocyclicalkenyl;    -   m) and mixtures thereof;        alternatively the R⁵ and R⁶ units can be taken together to form        a substituted or unsubstituted ring having in the ring from 3 to        10 carbon atoms; for example, R⁵ and R⁶ taken together can be        fused ring comprising ketones, inter alia, nootkatone; or        mono-cyclic ketones, inter alia, menthone, isomenthone, carvone,        and fenchone.

For the hydrolyzable ring pro-fragrances of the present invention eachR⁷ is independently selected from any substituted or unsubstitutedhydrocarbyl unit, non-limiting embodiments are selected from the groupconsisting of:

-   -   a) R⁶;    -   b) hydroxyl;    -   c) a carbonyl comprising unit having the formula:        —(CH₂)_(x)COR⁸        -   wherein R⁸ is:        -   i) —OH;        -   ii) —OR⁹ wherein R⁹ is hydrogen, C₁-C₁₅ substituted linear            alkyl, C₁-C₁₅ unsubstituted linear alkyl, C₁-C₁₅ substituted            branched alkyl, C11-C₁₅ unsubstituted branched alkyl, C₂-C₂₂            substituted or unsubstituted linear alkenyl, C₃-C₂₂            substituted or unsubstituted branched alkenyl, or mixtures            thereof, wherein said substitution is not halogen or            thioalkyl; R⁹ is methyl, R⁹ is hydrogen and Z is oxygen or            sulfur when an oxazolidine is formed from the methyl esters            of serine, threonine, cysteine, and the like;        -   iii) —N(R¹⁰)₂ wherein R¹⁰ is hydrogen, C₁-C₆ substituted or            unsubstituted linear alkyl, C₃-C₆ substituted or            unsubstituted branched alkyl, or mixtures thereof;        -   iv) C₁-C₂₂ substituted or unsubstituted linear alkyl;        -   v) C₁-C₂₂ substituted or unsubstituted branched alkyl;        -   vi) C₂-C₂₂ substituted or unsubstituted linear alkenyl;        -   vii) C₃-C₂₂ substituted or unsubstituted branched alkenyl;        -   viii) C₃-C₂₂ substituted or unsubstituted cycloalkyl;        -   ix) C₆-C₂₂ substituted or unsubstituted aryl;        -   x) C₆-C₂₂ substituted or unsubstituted heterocyclicalkyl;        -   xi) C₆-C₂₂ substituted or unsubstituted heterocyclicalkenyl;        -   the index x is from 0 to 22;    -   d) alkyleneoxy units having the formula:        —[C(R¹¹)₂]_(y)[C(R¹¹)₂C(R¹¹)₂O]_(z)R¹¹        -   wherein each R¹¹ is independently;        -   i) hydrogen;        -   ii) —OH;        -   iii) C₁-C₄ alkyl;        -   iv) or mixtures thereof;        -   two R¹¹ units can be taken together to form a C₃-C₆            spiroannulated ring, carbonyl unit, or mixtures thereof; y            has the value from 0 to 10, z has the value from 1 to 50;    -   e) and mixtures thereof;    -   any two R⁷ units can be taken together to form:        -   i) a carbonyl moiety;        -   ii) a C₃-C₆ spiroannulated ring;        -   iii) a heterocyclic aromatic ring comprising from 5 to 7            atoms;        -   iv) a non-heterocyclic aromatic ring comprising from 5 to 7            atoms;        -   v) a heterocyclic ring comprising from 5 to 7 atoms;        -   vi) a non-heterocyclic ring comprising from 5 to 7 atoms;        -   vii) or mixtures thereof; and            the index m is an integer from 1 to 3.

For example, each of the ring carbon atoms may have one or both of thehydrogen atoms substituted as defined herein above or taken together toform an aromatic or non-aromatic, carbocyclic or heterocyclic ring, forexample:

One iteration of this embodiment relates to oxazolidines having theformula:

wherein R⁶ is selected from the group consisting of hydrogen and methyl;each R⁷ is independently hydrogen, methyl, —C(O)OR⁹ and mixturesthereof; R⁹ is hydrogen, C₁-C₁₂ alkyl, and mixtures thereof.

The following is a non-limiting example of the oxazolidone embodiment ofthe present invention.

Hydrolysis based release of the fragrance raw material can proceed byway of any hydrolyzable pro-fragrance compound which is initiated by therelease of the pro-fragrance unit from a photo-labile pro-fragranceconjugate. For example, the ionone series of ketone fragrance rawmaterials, unlike the damascone series delivered by Type A Release, areformed into photo-labile pro-fragrance conjugates in which thephoto-labile unit is connected to a pro-fragrance unit consisting of apro-fragrance compound that is an imine or an enamine that arethemselves formed from the reaction of an aldehyde or ketone fragranceraw material with an amine compound. The imine- or iminium-basedpro-fragrance compounds are released upon activation of the conjugate.The following is an example of a photo-labile pro-fragrance conjugatethat is capable of releasing an enamine-based pro-fragrance compound ofthe present invention.

The Type B Release photo-activated pro-fragrances can also comprise asuitable linking group for example a compound having the formula:

Another type of Type B Release relates to aminals or ketals having, forexample, the formula:

which is capable of releasing an aldehyde or ketone fragrance rawmaterial having the formula R⁵CHO or R⁵R⁶CHO and an alcohol having theformula R′OH. R′OH can be a fragrance raw material or not a fragranceraw material depending on the needs of the formulator. A non-limitingexample of an aminal according to the present invention has the formula:

The formulator when using aminals to deliver two fragrance raw materialscan make use of the R³ nitrogen unit to control the release rate of thefragrance raw materials once the photo-labile unit has released thepro-fragrance component. The formulator can make use of the R³ nitrogenunit to control the physical properties of the photo-labilepro-fragrance conjugate. Such properties include, but are not limitedto, the ability of the conjugate to deposit on a desired surface in anaqueous wash environment.

A further example of Type B Release relates to conjugates which areactivated by the breaking of the bond between the photo-labile unit andthe pro-fragrance unit, wherein an intramolecular reaction ensues whichdisplaces a pro-fragrance compound which then hydrolyzes to release thefragrance raw material. A non-limiting general example is theamino-amide photo-labile pro-fragrance conjugate depicted in the schemebelow:1. A Photo-Isomerization Followed by a Pro-Fragrance CompoundElimination Step:

2. A Subsequent Cyclization Step:

3. A Final Elimination Step:

Fragrance Raw Materials

Mixtures of fragrance materials are known by those skilled in the art offragrances and perfumes as “accords”. The term “accord” as used hereinis defined as “a mixture of two or more ‘fragrance raw materials’ whichare artfully combined to impart a pleasurable scent, odor, essence, orfragrance characteristic”. For the purposes of the present invention“fragrance raw materials” are herein defined as compounds having amolecular weight of at least 100 g/mol and which are useful in impartingan odor, fragrance, essence, or scent either alone or in combinationwith other “fragrance raw materials”. For the purposes of the presentinvention, fragrance raw materials which comprise an amino unit can bedirectly attached to the photo-labile unit and, therefore, releaseddirectly without further reaction.

Typically “fragrance raw materials” comprise inter alia alcohols,ketones, aldehydes, esters, ethers, nitriles, and alkenes such asterpenes. A listing of common “fragrance raw materials” can be found invarious reference sources, for example, “Perfume and Flavor Chemicals”,Vols. I and II; Steffen Arctander Allured Pub. Co. (1994) and “Perfumes:Art, Science and Technology”; Müller, P. M. and Lamparsky, D., BlackieAcademic and Professional (1994) both incorporated herein by reference.

Examples of fragrance raw material ketones which are capable of beingreleased by the compounds of the present invention include1-(2,6,6-trimethylcyclohex-2-enyl)-2-butene-1-one (α-damascone),1-(2,6,6-trimethyl-cyclohex-1-enyl)-2-butene-1-one (β-damascone),1-(2-methylene-6,6-dimethyl-cyclohexanyl)-2-butene-1-one (γ-damascone),1-(2,6,6-trimethylcyclohex-3-enyl)-2-butene-1-one (δ-damascone),4-(2,6,6-trimethylcyclohex-2-enyl)-3-butene-2-one (α-ionone),4-(2,6,6-trimethylcyclohex-1-enyl)-3-butene-2-one (β-ionone),4-(2-methylene-6,6-dimethylcyclo-hexanyl)-3-butene-2-one(γ-ionone).

Aldehydes which are releasable from the photo-activated conjugates ofthe present invention include but are not limited to phenylacetaldehyde,p-methyl phenylacetaldehyde, p-isopropyl phenylacetaldehyde, methylnonylacetaldehyde, phenylpropanal, 3-(4-t-butylphenyl)-2-methyl propanal,3-(4-t-butylphenyl)-propanal, 3-(4-methoxyphenyl)-2-methylpropanal,3-(4-isopropylphenyl)-2-methylpropanal,3-(3,4-methylenedioxyphenyl)-2-methylpropanal,3-(4-ethylphenyl)-2,2-dimethylpropanal, phenylbutanal,3-methyl-5-phenylpentanal, hexanal, trans-2-hexenal, cis-hex-3-enal,heptanal, cis-4-heptenal, 2-ethyl-2-heptenal, 2,6-dimethyl-5-heptenal,2,4-heptadienal, octanal, 2-octenal, 3,7-dimethyloctanal,3,7-dimethyl-2,6-octadien-1-al, 3,7-dimethyl-1,6-octadien-3-al,3,7-dimethyl-6-octenal, 3,7-dimethyl-7-hydroxyoctan-1-al, nonanal,6-nonenal, 2,4-nonadienal, 2,6-nonadienal, decanal, 2-methyl decanal,4-decenal, 9-decenal, 2,4-decadienal, undecanal, 2-methyldecanal,2-methylundecanal, 2,6,10-trimethyl-9-undecenal, undec-10-enyl aldehyde,undec-8-enanal, dodecanal, tridecanal, tetradecanal, anisaldehyde,bourgenonal, cinnamic aldehyde, α-amylcinnam-aldehyde, α-hexylcinnamaldehyde, methoxy-cinnamaldehyde, citronellal,hydroxy-citronellal, isocyclocitral, citronellyl oxyacet-aldehyde,cortexaldehyde, cumminic aldehyde, cyclamen aldehyde, florhydral,heliotropin, hydrotropic aldehyde, lilial, vanillin, ethyl vanillin,benzaldehyde, p-methyl benzaldehyde, 3,4-dimethoxybenzaldehyde, 3- and4-(4-hydroxy-4-methyl-pentyl)-3-cyclohexene-1-carboxaldehyde,2,4-dimethyl-3-cyclohexene-1-carboxaldehyde,1-methyl-3-(4-methylpentyl)-3-cyclohexencarboxaldehyde,p-methylphenoxyacetaldehyde, and mixtures thereof.

Fragrance raw materials suitable for use in the present invention aredescribed in U.S. Pat. No. 5,919,752 Morelli et al., issued Jul. 6,1999; U.S. Pat. No. 6,013,618 Morelli et al., issued Jan. 11, 2000; U.S.Pat. No. 6,077,821 Morelli et al., issued Jun. 20, 2000; U.S. Pat. No.6,087,322 Morelli et al., issued Jul. 11, 2000; U.S. Pat. No. 6,114,302Morelli et al., issued Sep. 5, 2000; U.S. Pat. No. 6,177,389 Morelli etal., issued Jan. 23, 2001; all of which are incorporated herein byreference.

Odor Detection Threshold

For the purposes of the present invention the term “odor detectionthreshold” is defined as the level at which a fragrance raw material isperceptible to the average human. The odor detection threshold (ODT) ofthe compositions of the present invention are preferably measured bycarefully controlled gas chromatograph (GC) conditions as describedhereinbelow.

Determination of Odor Detection Thresholds is as follows. A gaschromatograph is characterized to determine the exact volume of materialinjected by a syringe, the precise split ratio, and the hydrocarbonresponse using a hydrocarbon standard of known concentration andchain-length distribution. The airflow rate in accurately measured and,assuming the duration of a human inhalation to last 0.02 minutes, thesampled volume is calculated. Since the precise concentration at thedetector at any point in time is known, the mass per volume inhaled isknown and hence the concentration of material. To determine whether amaterial has a threshold below 10 ppb, solutions are delivered to thesniff port at the back-calculated concentration. A panelist sniffs theGC effluent and identifies the retention time when odor is notice. Theaverage over all panelists determines the threshold of noticeability orODT. The necessary amount of analyte is injected onto the column toachieve a 10 ppb concentration at the detector. Typical gaschromatograph parameters for determining odor detection thresholds arelisted below.

GC: 5890 Series II with FID detector 7673 Auto sampler

Column: J&W Scientific DB-1, length 30 m, i.d. 0.25 mm, film thickness10m.

Split Injection: 17/1 split ratio

Autosampler: 1.13 □l/injection

Column flow: 1.10 mL/min

Air flow: 345 mL/min

Inlet temperature: 245° C.

Detector temperature: 285° C.

Temperature Information:

Initial temperature: 50° C.

Rate: 5° C./min

Final temperature: 280° C.

Final time: 6 min

Leading assumptions: 0.02 minutes per sniff and that GC air adds tosample dilution.

A general first procedure relates to the conversion of a startingmaterial having formula 1 to the aryl acrylamide photo-labilepro-fragrance 3 by way of the intermediate aryl acrylic acid 2 asdepicted in the following scheme:

In the case wherein X is equal to oxygen (coumarin derivatives) thepreparation begins with a von Pechmann condensation as in the example ofthe reaction of resorcinol with acetoacetic acid ethyl ester depicted inthe following scheme:

Coumarin syntheses are reviewed by Dean, F. M. “Naturally OccurringOxygen Ring Compounds”; Butterworths: London, 1963; p. 176.

Preparation of 3-(2,4-dihydroxy-phenyl)-acrylic acid (5) from7-hydroxy-chromen-2-one (4)

To a solution of 20% sodium sulfite (640 g) at 60° C. is added7-hydroxy-chromen-2-one (75.0 g, 0.416 mol). The reaction mixture iswarmed to 100° C. and stirred for 1.5 h. To this solution is addeddropwise 30% KOH solution (301 g). The stirred mixture is cooled to 0°C. and acidified by the slow and careful addition of concentrated HCl,keeping the solution temperature below 10° C. The colorless precipitateis separated by filtration, washed with water and dried for 12 h undervacuum at 45° C. The resulting 3-(2,4-dihydroxy-phenyl)-acrylic acid isa colorless solid (24.0 g) and is used without further purification.

EXAMPLE 1 Preparation of Triplal Oxazolidine Conjugate (7) Step (1)preparation of 2-(2,4-Dimethyl-cyclohex-3-enyl)-oxazolidine (6)

To a 0° C. stirred solution of 66 g (0.47 mol) triplal and 21 g sodiumsulfate in 150 mL of methanol is added 29 g (0.47 mol) of ethanolamine.The reaction is allowed to warm to room temperature. After stirring for24 h the mixture is cooled to 0° C. and the solids are removed viavacuum filtration through Celite. Evaporation of the solvent gives aclear, slightly yellow oil.

Step (2) preparation of1-[2-(2,4-Dimethyl-cyclohex-3-enyl)-oxazolidin-3-yl]-3-(2-hydroxy-phenyl)-propenone(7)

To a 0° C. solution of 8.2 g (0.050 mol) of o-hydroxy-trans-cinnamicacid in 500 mL of anhydrous tetrahydrofuran (THF) is added 10.3 g (0.050mol) of 1,3-dicyclohexylcarbodiimide (DCC). After stirring for 10 min,6.8 g (0.050 mol) of 1-hydroxybenzotriazole (HOBt), 8.2 g (0.045 mol) of2-(2,4-dimethyl-3-cyclohexen-1-yl)-1,3-oxazolidine and 1.1 g (0.009 mol)of 4-(dimethylamino)pyridine (DMAP) is added and stirred at 0° C. for 1h, warmed to room temperature and stirred for an additional 24 h. Themixture is cooled to 0° C., filtered and the solvent is removed invacuo. The residue is diluted with ethyl acetate and washed three timeswith saturated sodium bicarbonate, followed by 10% citric acid andbrine. The organic layer is dried over anhydrous magnesium sulfate,filtered and concentrated in vacuo. The product 7 is further purified byflash chromatography on basic alumina with 20:1 chloroform/methanol.

EXAMPLE 2 Preparation of dihydro-β-ionone Oxazine Conjugate (9) Step (1)preparation of2-Methyl-2-[2-(2,6,6-trimethyl-cyclohex-1-enyl)-ethyl]-[1,3]oxazinane(8)

To a 0° C. stirred solution of4-(2,6,6-trimethyl-cyclohex-1-enyl)-butan-2-one (25.2 g, 0.13 mol) andsodium sulfate (20 g) in 80 mL of methanol is added 3-amino-1-propanol(10 g, 0.13 mol). The reaction is allowed to warm to room temperature.After stirring for 24 h the mixture is cooled to 0° C. and the solidsare removed via vacuum filtration through Celite. Evaporation of thesolvent gives a clear yellow oil.

Step (2) preparation of3-(2,4-Dihydroxy-phenyl)-1-{2-methyl-2-[2-(2,6,6-trimethyl-cyclohex-1-enyl)-ethyl]-[1,3]oxazinan-3-yl}-but-2-en-1-one(9)

To a 0° C. solution of 11.1 g (0.050 mol) of3-(2,4-dihydroxy-phenyl)-3-methyl-acrylic acid in 500 mL of anhydrousTHF is added 10.3 g (0.050 mol) of DCC. After stirring for 10 min, 6.8 g(0.050 mol) of HOBt, 11.3 g (0.045 mol) of2-methyl-2-[2-(2,6,6-trimethyl-cyclohex-1-enyl)-ethyl]-[1,3]oxazinane(8) and 1.1 g (0.009 mol) of DMAP are added and stirred at 0° C. for 1h, warmed to room temperature and stirred for an additional 24 h. Themixture is cooled to 0° C., filtered and the solvent is removed invacuo. The residue is diluted with ethyl acetate and washed three timeswith saturated sodium bicarbonate, followed by 10% citric acid andbrine. The organic layer is dried over anhydrous magnesium sulfate,filtered and concentrated in vacuo. The product 9 is further purified byflash chromatography on basic alumina with 20:1 chloroform/methanol.

EXAMPLE 3 Preparation of δ-damascone Michael Adduct Conjugate (11) Step(1) Preparation of3-Amino-1-(2,6,6-trimethyl-cyclohex-3-enyl)-butan-1-one (10)

To a 0° C. stirred solution of 66.2 g (0.574 mol, 1.2 equiv) of1-(2,6,6-trimethyl-cyclohex-3-enyl)-but-2-en-1-one (8-damascone) in 250mL of ethanol is added 143.3 mL (1 equiv, 0.287 mol) of ammonia(Aldrich, 2.0 M in ethanol). The reaction is allowed to warm to roomtemperature. After stirring for 24 h, the ethanol is concentrated byrotary evaporation to give an oil consisting of 10.

Step (2) Preparation of3-(2,4-Dihydroxy-phenyl)-N-[1-methyl-3-oxo-3-(2,6,6-trimethyl-cyclohex-3-enyl)-propyl]-acrylamide(11)

To a solution of 3-amino-1-(2,6,6-trimethyl-cyclohex-3-enyl)-butan-1-one(2.38, 11.3 mmol, 10) and triethylamine (2.30 g, 22.6 mmol) in anhydrousTHF (150 mL) stirred for 5 min at 22° C. is added3-(2,4-dihydroxyphenyl)-acrylic acid (2.04 g, 11.3 mmol). To thisheterogeneous solution is added BOP Reagent (5.00 g, 11.3 mmol; Aldrich#22,608-4) in DMF (10 mL), and the subsequent homogeneous reactionmixture is stirred for 1 h. The reaction mixture is partitioned betweenether (200 mL) and water (400 mL); the organic layer is removed andwashed with ether (200 mL). The combined organic layers are washedsequentially with saturated sodium bicarbonate solution (200 mL) andbrine (200 mL). The organic layer is dried over anhydrous magnesiumsulfate, vacuum filtered and concentrated to give3-(2,4-dihydroxy-phenyl)-acrylic acid 1,5-dimethyl-1-vinyl-hex-4-enylester as an oil that is purified by flash chromatography to give 11 as acolorless solid.

EXAMPLE 4 Preparation of bis-8-damascone Michael Adduct Conjugate (15)

Step (1) To a 0° C. stirred solution of 96 g (0.50 mol) of1-(2,6,6-trimethyl-cyclohex-3-enyl)-but-2-en-1-one (δ-damascone) in 250mL of ethanol is added 47 g (0.25 mol) ofN¹-[3-(3-Amino-propylamino)-propyl]-propane-1,3-diamine. The reaction isallowed to warm to room temperature. After stirring for 24 h, theethanol is concentrated by rotary evaporation to give3-[3-(3-{3-[1-methyl-3-oxo-3-(2,6,6-trimethyl-cyclohex-3-enyl)-propylamino]-propylamino}-propylamino)-propylamino]-1-(2,6,6-trimethyl-cyclohex-3-enyl)-butan-1-one(bis-Michael adduct 14) as an oil.

Step (2) which is conversion of starting material 12 to intermediate 13can be a accomplished by the method described in Synthetic Comm. 1991,21, 351 included herein by reference.

Step (3) conversion of intermediate 13 to 15.

A solution of intermediate 13 (1.2 g, 3.7 mmol), thionyl chloride (2equiv, 0.88 g, 7.4 mmol, 0.54 mL) in anhydrous toluene (50 mL) isrefluxed for 3 h under an inert atmosphere. The reaction mixture isevaporated to dryness under vacuum and to the crude acid chloride isadded another portion of toluene (50 mL). Bis-Michael adduct 14 (1.1 g,1.9 mmol) is added and the reaction mixture is allowed to stir for 12 h.The mixture is diluted with toluene (100 mL) and washed with 100 mLportions of 1 N HCl, water and brine. The organic layer is dried overanhydrous magnesium sulfate, filtered and concentrated to giveacyl-protected 15. Removal of the acetoxy units by the method ofSynthetic Comm. 1991, 21, 351, incorporated herein by reference, affords15.

FORMULATIONS

The present invention relates to a photo-labile fragrance deliverysystem which delivers a photo-labile pro-fragrance conjugate. Thepro-fragrance relies upon the photo-initiated cascade to deliver thefragrance raw material. Because it is not necessary that thepro-fragrance compound immediately begins releasing an aldehyde orketone once the photo-labile unit has released said pro-fragrancecompound, the formulator may form a wide array of delivery systems. Ingeneral, the systems of the present invention comprise severalembodiments having various ranges of pro-fragrance conjugate, forexample:

-   -   a) from about 0.001% to about 5%, another embodiment comprises        from about 0.005% to about 1%, a range of from about 0.01% to        about 0.2% encompasses yet another embodiment, while a further        embodiment comprises from about 0.02% to about 0.1% by weight,        of a photo-activated pro-fragrance conjugate, said conjugate        comprising:        -   i) a photo-labile unit which upon exposure to            electromagnetic radiation is capable of releasing a            pro-fragrance unit as a pro-fragrance compound; and        -   ii) a pro-fragrance compound, which when so released is            capable of releasing a fragrance raw material; and

Another aspect of the present invention relates to conjugates of thepresent invention that comprise a photo-labile pro-fragrance conjugatecomprising a photo-labile unit which upon exposure to electromagneticradiation is capable of releasing a pro-fragrance unit as a fragrancecompound.

-   -   b) the balance carriers and adjunct ingredients.

The photo-labile pro-fragrances of the present invention have wideutility in perfumes and fine fragrances. This embodiment of the presentinvention comprises:

-   -   A) from about 0.001% by weight, of one or more photo-activated        pro-fragrance conjugates, said conjugates each comprising:        -   a) a photo-labile unit which upon exposure to            electromagnetic radiation is capable of releasing a            pro-fragrance unit;        -   b) a pro-fragrance unit, which when so released is either            -   i) a pro-fragrance compound capable of releasing a                fragrance raw material; or            -   ii) a fragrance raw material;    -   B) from about 0.01% to about 99% by weight, of an admixture of        fragrance raw material; and    -   C) the balance carriers and adjunct ingredients.

Typically the carrier for fine fragrances and perfumes is ethanol orethanol/water. In addition to the photo-labile conjugates of the presentinvention, other pro-fragrances, pro-accords, and the like can beincluded, especially species which take advantage of the differential pHof skin. For example, acid labile pro-fragrances include orthoesters,acetals, ketals, and the like. Therefore, the combination of aphoto-labile pro-fragrance and an acid labile pro-fragrance whichreleases the same fragrance raw material, inter alia, damascone,citronellal, is one aspect encompassed by the present invention.

For the purposes of the present invention the terms “perfume” and “finefragrance” are essentially synonymous and are used collectively orinterchangeably throughout the present specification and are taken tomean the more concentrated forms of fragrance-containing compositions.Aspects of the present invention which apply to “perfumes” willtherefore apply equally to “fine fragrances” and vice versa. Typically,colognes, eau de toilettes, after shaves, and other fragrance-containingembodiments are perfumes or fine fragrances which have a greater degreeof dilution, usually by a volatile carrier such as ethanol.

EMBODIMENTS

The following are additional non-limiting embodiments of the presentinvention.

Skin Conditioning Lotions

An example of a skin care composition of the present invention comprisesan ester having a total number of carbon atoms in excess of about 28,for example lauryl laurate, lauryl myristate, myristyl myristate,behenyl caprate, cetearyl palmitate, behenyl stearate, more preferablycetearyl palmitate and cetyl stearate.

The present compositions in addition to the esters described hereinabove, contain an emollient material in an amount such that the amountof ester plus emollient is from about 0.2%, preferably from about 4% toabout 25%, preferably to about 18% of the total composition. Onefunction of the emollient is to ensure that the ester is plasticizedsufficiently to allow it to be in a film-like state on the skin. Theemollient in the present compositions is selected from the groupconsisting of fatty alcohols, esters having fewer than about 24 totalcarbon atoms (e.g. isopropyl palmitate), branched chain esters havinggreater than about 24 total carbon atoms (e.g. cetearyl octonate),squalane, liquid or solid paraffins, mixtures of fatty acids andsqualane, mixtures of fatty acids and liquid or solid paraffins andmixtures thereof. The aforementioned esters, those having fewer than 24carbon atoms or branched and having more than 24 carbon atoms, if usedas an emollient should preferably be used in an mount equal to about athird of the long chain ester. The particular emollient selected dependsin part on the particular ester selected since proper plasticization, asindicated above, is desired. The emollient for the esters having morethan 28 carbon atoms is preferably selected from the group consisting ofsqualane, liquid or solid paraffins and mixtures of fatty alcohols withsqualane or paraffins. Typical fatty alcohols and fatty acids useful inthe present compositions include those having from 12-22 carbon atomssuch as cetyl alcohol, myristyl alcohol, stearyl alcohol, stearic acidand palmitic acid. Paraffins include, for example, mineral oil,petrolatum and paraffin wax. It is preferred that distilled water beused in the present compositions.

Optional Components

Oil Phase Components

In addition to the long chain esters, emollients and emulsifiersdescribed previously, the oil phase of the present compositions maycontain a variety of materials including:

(a) Esters not meeting the requirements for the long chain ester and notpresent as an emollient, supra, such as oleyl oleate, isostearylisostearate, isopropyl lanolate, isopropyl myristate, butyl stearate,myristyl lactate and 2-ethyl hexyl palmitate;

(b) Oils such as castor oil, jojoba oil, cottonseed oil, peanut oil andsesame oil;

(c) Waxes such as ceresin wax, carnuba wax, beeswax and castor wax;

(d) Lanolin, its derivatives and components such as acetylated lanolin,lanolin alcohols and lanolin fatty acids. Lanolin fatty acids aredescribed in U.S. Pat. No. Re. 29,814, Oct. 24, 1978 to W. E. Snyderincorporated herein by reference.

(e) Polyalkylenes such as hydrogenated polyisobutene and polyethylene;and

(f) Sterols such as cholesterol and phytosterol.

These optional oil phase materials may comprise up to about 80% of theoil phase, preferably up to about 35%. When used at these levels, theoptional components do not impair the occlusive nature of thecompositions and add to the composition's total cosmetic performance.

Water Phase Components

The water phase of the compositions may contain many different materialsincluding:

(a) Humectants, such as sorbitol, glycerine, propylene glycol,alkoxylated glucose and hexanetriol at a level of from about 1% to about20%.

(b) Thickening agents such as carboxyvinyl polymers, ethyl cellulose,polyvinyl alcohol, carboxymethyl cellulose, vegetable gums and clayssuch as Veegum.®. (magnesium aluminum silicate, R. T. Vanderbilt, Inc.)at a level of from about 0.01% to about 6%;

(c) Proteins and polypeptides at a level of from about 0.1% to about 3%;

(d) Preservatives such as the methyl, ethyl, propyl and butyl esters ofhydroxybenzoic acid (Parabens-Mallinckrodt Chemical Corporation) EDTAand imidazolidinyl urea (Germall 115-Sutton Laboratories) at a level offrom about 0.2% to about 2.5%; and

(e) An alkaline agent such as sodium hydroxide to neutralize, ifdesired, part of the fatty acids or thickener which may be present.

All of the percentages of these additional water phase components are ofthe total composition.

The present compositions may also contain agents suitable for aestheticpurposes such as dyes. The compositions of the present invention arepreferably substantially free of materials that adversely affect theirperformance. Therefore, such things as polyethylene glycols arepreferably present only at levels below about 1% of the totalcomposition. The pH of the present compositions is preferably in therange of about 7.5-10.

Method of Manufacture

The compositions which comprise the skin lotion embodiments of thepresent invention generally have a lotion consistency and may be in theform of oil-in-water or water-in-oil emulsions with the former beingpreferred because of their more pleasing cosmetic properties. Thecompositions of the present invention are preferably made by the methodcomprising the steps of;

a) preparing the oil phase;

b) preparing the water phase; and

c) adding the oil phase to the water phase.

Step (a) is carried out by heating the oil phase materials to atemperature of about 75° C. to about 10° C. Step (b) is carried out byheating the water phase materials to a temperature about the same asthat of the oil phase. The emulsion is formed by slowly adding the oilphase prepared in step (a) to the water phase prepared in step (b) withstirring. The pro-accords which comprise the fragrance delivery systemor other ingredients may be added to the phase in which they are solubleprior to the mixing of the two phases or added directly to the mixedwater and oil phases.

In addition to the fragrance-containing compositions for use on humanskin, the pro-accords of the present invention are also suitable for usein any odor controlling or fragrance mediating application. An exampleof this odor control capacity is animal litter and odor control articlesuseful in lining the cages, stalls, and other living areas ofdomesticated animals. For example, U.S. Pat. No. 5,339,769 Toth et al.,issued Aug. 23, 1994 describes a process for making an absorbentcomposition, which can well accommodate the pro-accord materials of thepresent invention.

An example of a suitable litter material which comprises thephoto-labile pro-fragrance conjugates of the present invention can beformed by the following process.

A Glatt fluid bed granulator is charged with 1,0000 g of bentonite clay(90% of the particles being greater than 420 microns) and 10 g of acellulose ether (Methocel™ K15M Premium, a cellulose ether having aviscosity of 15,000 centipoise (cps) as a 2% aqueous solution). Thegranulator is started and the product temperature is brought up to about4° C. (outlet temperature). When the outlet temperature reaches about 4°C., atomized water is sprayed onto the moving powders within thegranulator, During the granulation process, inlet air temperature ismaintained at 70° C. to 80° C.; air atomization pressure is 28-35 psi;and the spraying cycle is for 45 seconds with a 15 second shaking time.

The clay/cellulose ether agglomerates swell over time. The waterhydrates the cellulose ether polymer, which produces adhesion to formthe granule. At this time it is more advantageous to introduce thepro-accord materials and other aesthetic fragrances. The formation ofthe granule promotes aggregation of the small sized particles of theinert substrate, e.g. clay particles of about 50 to 600 microns. Theformation of a granule significantly reduces the quality of dust in thefinal product while the litter forms an agglomerate when wetted.

In an alternative embodiment of the clay-based litter boxarticles/pro-accord admixture, once the clay particles have been formed,a concentrated solution, or a carrier alcohol-based admixture of thepro-accords may be delivered to the surface of the granule by a suitablemeans.

A deodorant gel stick of the present invention having the compositiongiven below, and being essentially free of water, is prepared asfollows. TABLE I weight % Ingredients 5 6 7 8 Dipropylene glycol 39.8551.95 75.10 71.15 Sodium Stearate 5.50 5.50 5.50 5.55 PPG-3 myristylether 29.40 25.33 15.00 19.30 Cyclomethicone-D5 21.00 13.33 — — Ethanol(absolute; 200 proof) 1.80 1.44 1.95 1.50 Zinc pyrithione¹ 0.05 0.050.05 0.10 Conjugate² 2.40 0.55 0.1 0.001¹Powder form commercially available from Olin.²Photo-labile pro-fragrance conjugate according to Example 1.

All of the above materials, except the fragrance pro-accord, arevigorously mixed and heated to about 121° C. until the mixture is clear.The mixture is then cooled to about 8° C. and the pro-accord is addedwith stirring. The mixture is poured into stick molds and cooled to roomtemperature forming the deodorant gel stick compositions of the presentinvention.

A personnel cleanser composition is prepared by combining the followingingredients using conventional mixing techniques. TABLE II weight %Ingredients 9 10 11 12 Phase A Water QS 100 QS 100 QS 100 QS 100Disodium EDTA 0.100 0.100 0.100 0.100 Glycerin 4.00 4.00 4.00 4.00Methylparaben 0.200 0.200 0.200 0.200 C₁₀-C₃₀ 0.150 0.150 0.150 0.150alkyl acrylate crosspolymer¹ Carbomer 954² 0.250 0.250 0.250 0.250 WaterQS 100 QS 100 QS 100 QS 100 Phase B Stearic Acid 0.110 0.110 0.110 0.110Stearyl alcohol 0.875 0.875 0.875 0.875 Cetyl alcohol 0.875 0.875 0.8750.875 Propylparaben 0.150 0.150 0.150 0.150 Steareth-2 — 0.25 0.25 0.25Steareth-21 — 0.50 0.50 0.50 Phase C Sodium hydroxide³ 0.130 0.130 0.1300.130 Phase D Diisopropyl sebacate 1.50 1.50 1.50 1.50 Isohexadecane5.00 2.00 5.00 5.00 Mineral Oil⁴ — 5.00 — — Phase E Phenoxyethanol 0.50.5 — 0.5 Conjugate⁵ 1.5 1.5 — — Conjugate⁶ — — 2.20 1.5 Phase F Glucoseamide 0.96 0.96 0.96 0.96 Minors, aesthetics, balance balance balancebalance carriers¹Available as Pemulen ® from B. F. Goodrich Corporation.²Available as Carbomer ® 954 from B. F. Goodrich Corporation.³As a 50% aqueous solution.⁴Light mineral oil available as Drakeol 5 from Penreco, Dickenson, TX.⁵Photo-labile pro-fragrance conjugate according to Example 1.⁶Photo-labile pro-fragrance conjugate according to Example 2.The above Examples 8-11 can be suitably prepared as follows. In asuitable vessel, the Phase A ingredients are mixed at room temperatureto form a dispersion and heated with stirring to 70-80° C. In a separatevessel, the Phase B ingredients are heated with stirring to 70-80° C.Phase B is then added to Phase A with mixing to form the emulsion. Next,Phase C is added to neutralize the composition. The Phase D ingredientsare added with mixing, followed by cooling to 45-50° C. The Phase Eingredients are then added with stirring, followed by cooling to 40° C.Phase F is heated with mixing to 40° C. and added to the emulsion, whichis cooled to room temperature. The resulting cleansing composition isuseful for cleansing the skin. The emulsion de-emulsifies upon contactwith the skin.

The present invention further relates to the use of photo-labilepro-fragrances in embodiments which do not contact human skin, interalia, laundry detergent compositions, hard surface cleaningcompositions, carpet cleaning compositions, and the like.

Surfactant System

The laundry detergent compositions of the present invention comprise asurfactant system. The surfactant systems of the present invention maycomprise any type of detersive surfactant, non-limiting examples ofwhich include one or more mid-chain branched alkyl sulfate surfactants,one or more mid-chain branched alkyl alkoxy sulfate surfactants, one ormore mid-chain branched aryl sulfonate surfactants, one or more nonmid-chain branched sulphonates, sulphates, cationic surfactants,zwitterionic surfactants, ampholytic surfactants, and mixtures thereof.

The total amount of surfactant present in the compositions of thepresent invention is from about 10% by weight, in one embodiment of thepresent invention the range of surfactant is from about 10% to about 80%by weight, of said composition. Another embodiment the amount ofsurfactant is from about 10% to about 60%, wherein another embodimentcomprises from about 15% to about 30% by weight, of said composition.

Nonlimiting examples of surfactants useful herein include:

-   a) C₁₁-C₁₈ alkyl benzene sulfonates (LAS);-   b) C₆-C₁₈ mid-chain branched aryl sulfonates (BLAS);-   c) C₁₀-C₂₀ primary, α or ω-branched, and random alkyl sulfates (AS);-   d) C₁₄-C₂₀ mid-chain branched alkyl sulfates (BAS);-   e) C₁₀-C₁₈ secondary (2,3) alkyl sulfates as described in U.S. Pat.    No. 3,234,258 Morris, issued Feb. 8, 1966; U.S. Pat. No. 5,075,041    Lutz, issued Dec. 24, 1991; U.S. Pat. No. 5,349,101 Lutz et al.,    issued Sep. 20, 1994; and U.S. Pat. No. 5,389,277 Prieto, issued    Feb. 14, 1995 each incorporated herein by reference;-   f) C₁₀-C₁₈ alkyl alkoxy sulfates (AEXS) wherein preferably x is from    1-7;-   g) C₁₄-C₂₀ mid-chain branched alkyl alkoxy sulfates (BAE_(x)S);-   h) C₁₀-C₁₈ alkyl alkoxy carboxylates preferably comprising 1-5    ethoxy units;-   i) C₁₂-C₁₈ alkyl ethoxylates, C₆-C₁₂ alkyl phenol alkoxylates    wherein the alkoxylate units are a mixture of ethyleneoxy and    propyleneoxy units, C₁₂-C₁₈ alcohol and C₆-C₁₂ alkyl phenol    condensates with ethylene oxide/propylene oxide block polymers inter    alia Pluronic® ex BASF which are disclosed in U.S. Pat. No.    3,929,678 Laughlin et al., issued Dec. 30, 1975, incorporated herein    by reference;-   j) C₁₄-C₂₂ mid-chain branched alkyl alkoxylates, BAE_(x);-   k) Alkylpolysaccharides as disclosed in U.S. Pat. No. 4,565,647    Llenado, issued Jan. 26, 1986, incorporated herein by reference;-   l) Pseudoquat surfactants having the formula:    -   wherein R is C₄-C₁₀ alkyl, R¹ is selected from the group        consisting of C₁-C₄ alkyl, —(CH₂CHR²⁰)_(y)H, and mixtures        thereof; R² is hydrogen, ethyl, methyl, and mixtures thereof; y        is from 1 to 5; x is from 2 to 4; for the purposes of the        present invention, a particularly useful pseudoquat surfactant        comprises R equal to an admixture of C₈-C₁₀ alkyl, R¹ is equal        to methyl; and x equal to 3; these surfactants are described in        U.S. Pat. No. 5.916,862 Morelli et al., issued Jun. 29, 1999        included herein by reference;-   m) Polyhydroxy fatty acid amides having the formula:    wherein R⁷ is C₅-C₃₁ alkyl; R⁸ is selected from the group consisting    of hydrogen, C₁-C₄ alkyl, C₁-C₄ hydroxyalkyl, Q is a    polyhydroxyalkyl moiety having a linear alkyl chain with at least 3    hydroxyls directly connected to the chain, or an alkoxylated    derivative thereof; preferred alkoxy is ethoxy or propoxy, and    mixtures thereof. These surfactants are described in U.S. Pat. No.    5,489,393 Connor et al., issued Feb. 6, 1996; and U.S. Pat. No.    5,45,982 Murch et al., issued Oct. 3, 1995, both incorporated herein    by reference.

The mid-chain branched alkyl sulfate surfactants of the presentinvention have the formula:

the alkyl alkoxy sulfates have the formula:

the alkyl alkoxylates have the formula:

wherein R, R¹, and R² are each independently hydrogen, C₁-C₃ alkyl, andmixtures thereof; provided at least one of R, R¹, and R² is nothydrogen; preferably R, R¹, and R² are methyl; preferably one of R, R¹,and R² is methyl and the other units are hydrogen. The total number ofcarbon atoms in the mid-chain branched alkyl sulfate and alkyl alkoxysulfate surfactants is from 14 to 20; the index w is an integer from 0to 13; x is an integer from 0 to 13; y is an integer from 0 to 13; z isan integer of at least 1; provided w+x+y+z is from 8 to 14 and the totalnumber of carbon atoms in a surfactant is from 14 to 20; R³ is C₁-C₄linear or branched alkylene, preferably ethylene, 1,2-propylene,1,3-propylene, 1,2-butylene, 1,4-butylene, and mixtures thereof.

M denotes a cation, preferably hydrogen, a water soluble cation, andmixtures thereof. Non-limiting examples of water soluble cations includesodium, potassium, lithium, ammonium, alkyl ammonium, and mixturesthereof.

Adjunct Ingredients

The following are non-limiting examples of adjunct ingredients useful inthe laundry compositions of the present invention, said adjunctingredients include builders, optical brighteners, soil releasepolymers, dye transfer agents, dispersents, enzymes, suds suppressers,dyes, perfumes, colorants, filler salts, hydrotropes, photoactivators,fluorescers, fabric conditioners, hydrolyzable surfactants,preservatives, anti-oxidants, chelants, stabilizers, anti-shrinkageagents, anti-wrinkle agents, germicides, fungicides, anti corrosionagents, and mixtures thereof.

The following are non-limiting examples of laundry detergentcompositions according to the present invention. TABLE III weight %Ingredients 13 14 15 16 Polyhydroxy coco- 2.50 4.00 4.50 — fatty acidamide NEODOL 24-7¹ — 4.50 — — NEODOL 23-9² 0.63 — 4.50 2.00 C₁₅ Alkyl20.15 4.00 5.50 20.50 ethoxylate sulphate C₂₅ Alkyl — 14.00 15.00 —sulfate C_(11.8) linear — — — 6.00 alkylbenzene sulfonate C₈-C₁₀ — 1.30— — Amidopropyl Amine C₁₀ Amidopropyl 0.50 — — 1.50 Amine Citric acid3.00 2.00 3.00 2.50 C₁₂-C₁₈ 2.00 6.50 5.00 5.00 fatty acid Rapeseedfatty acid — 4.10 — 6.50 Ethanol 3.36 1.53 5.60 0.50 Propanediol 7.409.20 6.22 4.00 Monoethanolamine 1.00 7.90 8.68 0.50 Sodium hydroxide2.75 1.30 0.75 4.40 Sodium p-toluene 2.25 — 1.90 — sulfonate Borax/Boricacid 2.50 2.00 3.50 2.50 Protease³ 0.88 0.74 1.50 0.88 Lipolase⁴ — 0.120.18 — Duramyl⁵ 0.15 0.11 — 0.15 CAREZYME 0.053 0.028 0.080 0.053Dispersant⁶ 0.60 0.70 1.50 0.60 Ethoxylated 1.20 0.70 1.50 1.20polyalkyleneimine⁷ Optical Brightener 0.13 0.15 0.30 0.15 Conjugate⁸ 1.01.5 0.2 0.02 Pro-perfume⁹ 0.01 — 0.005 — Suds suppresser 0.12 0.28 0.120.12 Minors, aesthetics, balance balance balance balance stabilizers,water¹C₁₂-C₁₄ alkyl ethoxylate as sold by Shell Oil Co.²C₁₂-C₁₃ alkyl ethoxylate as sold by Shell Oil Co.³Protease B variant of BPN' wherein Tyr 17 is replaced with Leu.⁴Derived from Humicola lanuginosa and commercially available from Novo.⁵Disclosed in WO 9510603 A and available from Novo.⁶Hydrophilic dispersant PEI 189 E₁₅-E₁₈ according to U.S. 4,597,898,Vander Meer, issued Jul. 1, 1986.⁷Polyalkyleneimine dispersant PEI 600 E₂₀.⁸Photo-labile pro-fragrance conjugate according to Example 3.⁹Pro-perfume: 3-Amino-1-(2,6,6-trimethyl-cyclohex-3-enyl)-butan-1-one(10) according to Example 3.

As a non-limiting example, granular compositions are generally made bycombining base granule ingredients, e.g., surfactants, builders, water,etc., as a slurry, and spray drying the resulting slurry to a low levelof residual moisture (5-12%). The remaining dry ingredients, e.g.,granules of the polyalkyleneimine dispersant, can be admixed in granularpowder form with the spray dried granules in a rotary mixing drum. Theliquid ingredients, e.g., solutions of the polyalkyleneimine dispersant,enzymes, binders and perfumes, can be sprayed onto the resultinggranules to form the finished detergent composition. Granularcompositions according to the present invention can also be in “compactform”, i.e. they may have a relatively higher density than conventionalgranular detergents, i.e. from 550 to 950 g/l. In such case, thegranular detergent compositions according to the present invention willcontain a lower amount of “inorganic filler salt”, compared toconventional granular detergents; typical filler salts are alkalineearth metal salts of sulphates and chlorides, typically sodium sulphate;“compact” detergents typically comprise not more than 10% filler salt.

Liquid detergent compositions can be prepared by admixing the essentialand optional ingredients thereof in any desired order to providecompositions containing components in the requisite concentrations.Liquid compositions according to the present invention can also be in“compact form”, in such case, the liquid detergent compositionsaccording to the present invention will contain a lower amount of water,compared to conventional liquid detergents. Addition of thepolyalkyleneimine dispersant to liquid detergent or other aqueouscompositions of this invention may be accomplished by simply mixing intothe liquid solutions the polyalkyleneimine dispersant.

The compositions of the present invention can be suitably prepared byany process chosen by the formulator, non-limiting examples of which aredescribed in U.S. Pat. No. 5,691,297 Nassano et al., issued Nov. 11,1997; U.S. Pat. No. 5,574,005 Welch et al., issued Nov. 12, 1996; U.S.Pat. No. 5,569,645 Dinniwell et al., issued Oct. 29, 1996; U.S. Pat. No.5,565,422 Del Greco et al., issued Oct. 15, 1996; U.S. Pat. No.5,516,448 Capeci et al., issued May 14, 1996; U.S. Pat. No. 5,489,392Capeci et al., issued Feb. 6, 1996; U.S. Pat. No. 5,486,303 Capeci etal., issued Jan. 23, 1996 all of which are incorporated herein byreference.

The following are non-limiting examples of malodor abatementcompositions utilizing the photo-labile conjugates of the presentinvention. TABLE IV weight % Ingredients 17 18 19 20 α-Cyclodextrin 0.50— 0.50 — Hydroxy γ-cyclodextrin — 1.00 — — Methylated β- — — 0.50 —cyclodextrin Hydroxypropyl α- — — — 0.27 cyclodextrin Hydroxypropyl β-1.00 2.50 — 0.73 cyclodextrin γ-Cyclodextrin 0.50 1.00 — —Anti-microbial¹ 0.001 — 0.0008 0.008 Zinc chloride — — 1.0 1.0Glutaraldehyde — 0.01 — — Ethanol — 2.00 — — Propylene glycol — — — 0.06Conjugate² 1.5 0.2 0.01 0.002 Distilled water balance balance balancebalance¹Kathon ® ICP/CG II (Rohm & Haas).²According to Example 4.

The above compositions 16-19 can be prepared or used according to any ofU.S. Pat. No. 5,534,165 Pilosof et al., issued Jul. 9, 1996; U.S. Pat.No. 5,593,670 Trinh et al., issued Jan. 14, 1997; U.S. Pat. No.5,686,097 Trinh et al., issued Sep. 16, 1997; U.S. Pat. No. 5,714,137Trinh et al. issued Feb. 3, 1998; U.S. Pat. No. 5,939,060 Trinh et al.,issued Aug. 17, 1999; U.S. Pat. No. 6,146,621 Trinh et al., issued Nov.14, 2000; all of which are included herein by reference.

The following is a fine fragrance accord suitable for use in a finefragrance or perfume which comprises a photo-labile conjugate accordingto the present invention. TABLE V weight % Ingredients 21 22 23 24Pro-fragrance component Pro-fragrance¹ 1.0 — — — Pro-fragrance² 2.0 — —— Pro-fragrance³ 2.0 — — — Pro-fragrance⁴ 2.0 — — — Pro-fragrance⁵ 0.9 —— — Free fragrance component Damascone 0.0001 — — 0.001 Melonal 0.05 — —0.002 Triplal 0.01 — — 0.002 Undecavertol — — — 0.001 Geraniol — — —0.004 Additional free 13.8 15.2 17.0 15.1 fragrance raw materials⁶Photo-labile pro-fragrance conjugate component Conjugate⁷ 2.0 0.4 0.010.2 Conjugate⁸ — 0.4 0.02 0.08 Conjugate⁹ — 0.4 0.03 0.08 Carrier¹⁰balance balance balance balance¹Pro-fragrance according to U.S. Pat. No. 6,013,618 Morelli et al.,issued Jan. 11, 2000, U.S. Pat. No. 6,077,821 Morelli et al., issuedJun. 20, 2000 or U.S. Pat. No. 6,087,322 Morelli et al., issued Jul. 11,2000 which releases delta-damascone.²Pro-fragrance according to U.S. Pat. No. 6,013,618 Morelli et al.,issued Jan. 11, 2000, U.S. Pat. No. 6,077,821 Morelli et al., issuedJun. 20, 2000 or U.S. Pat. No. 6,087,322 Morelli et al., issued Jul. 11,2000 which releases melonal.³Pro-fragrance according to U.S. Pat. No. 6,013,618 Morelli et al.,issued Jan. 11, 2000, U.S. Pat. No. 6,077,821 Morelli et al., issuedJun. 20, 2000 or U.S. Pat. No. 6,087,322 Morelli et al., issued Jul. 11,2000 which releases triplal.⁴Pro-fragrance according to U.S. Pat. No. 6,013,618 Morelli et al.,issued Jan. 11, 2000, U.S. Pat. No. 6,077,821 Morelli et al., issuedJun. 20, 2000 or U.S. Pat. No. 6,087,322 Morelli et al., issued Jul. 11,2000 which releases undecavertol.⁵Pro-fragrance according to U.S. Pat. No. 6,013,618 Morelli et al.,issued Jan. 11, 2000, U.S. Pat. No. 6,077,821 Morelli et al., issuedJun. 20, 2000 or U.S. Pat. No. 6,087,322 Morelli et al., issued Jul. 11,2000 which releases geraniol.⁶Conventional fragrance accord.⁷Photo-labile pro-fragrance conjugate according to Example 3.⁸Photo-labile pro-fragrance conjugate having the formula:

⁹Photo-labile pro-fragrance conjugate having the formula:

¹⁰Ethanol: water mixture (between 100:0 and 50:50).

The following are non-limiting examples of shampoo and hair conditioningcompositions according to the present invention. TABLE VI weight %Ingredients 25 26 27 28 Ammonium Laureth-3 14.00 14.00 14.00 14.00Sulfate Cocamidopropyl 2.70 2.70 2.70 2.70 betaine Polyquaternium-100.15 0.15 0.15 0.30 Light mineral oil 0.30 0.15 0.05 0.30 Cocamide MEA0.80 0.80 0.80 0.80 Cetyl alcohol 0.42 0.42 0.42 0.42 Stearyl alcohol0.18 0.18 0.18 0.18 Ethylene glycol 1.50 1.50 1.50 1.50 distearateDimethicone 1.00 1.00 1.00 3.00 DMDM hydantoin 0.37 0.37 0.37 0.37Additional free 0.35 0.45 0.60 1.0 fragrances Conjugate¹ 0.001 0.05 0.51.50 Distilled water balance balance balance balance¹According to Example 3.

The dimensions and values disclosed herein are not to be understood asbeing strictly limited to the exact numerical values recited. Instead,unless otherwise specified, each such dimension is intended to mean boththe recited value and a functionally equivalent range surrounding thatvalue. For example, a dimension disclosed as “40 mm” is intended to mean“about 40 mm”.

All documents cited in the Detailed Description of the Invention are, inrelevant part, incorporated herein by reference; the citation of anydocument is not to be construed as an admission that it is prior artwith respect to the present invention.

While particular embodiments of the present invention have beenillustrated and described, it would be obvious to those skilled in theart that various other changes and modifications can be made withoutdeparting from the spirit and scope of the invention. It is thereforeintended to cover in the appended claims all such changes andmodifications that are within the scope of this invention.

1. A photo-labile pro-fragrance conjugate having the formula:

wherein R is an oxazolidine unit capable of releasing a fragrance rawmaterial having the formula:

wherein R⁵ units are selected from: a) C₆-C₂₂ substituted orunsubstituted linear alkyl b) C₆-C₂₂ substituted or unsubstitutedbranched alkyl; c) C₆-C₂₂ substituted or unsubstituted linear alkenyl;d) C₆-C₂₂ substituted or unsubstituted branched alkenyl; e) C₆-C₂₂substituted or unsubstituted cycloalkyl; f) C₆-C₂₂ substituted orunsubstituted branched cycloalkyl; g) C₆-C₂₂ substituted orunsubstituted cycloalkenyl; h) C₆-C₂₂ substituted or unsubstitutedbranched cycloalkenyl; i) C₆-C₂₂ substituted or unsubstituted aryl; j)C₆-C₂₂ substituted or unsubstituted heterocyclicalkyl; k) C₆-C₂₂substituted or unsubstituted heterocyclicalkenyl; l) and mixturesthereof; R⁶ is selected from the group consisting of hydrogen andmethyl; each R⁷ is independently hydrogen, methyl or —C(O)OR⁹, andmixtures thereof; R⁹ is hydrogen, C₁-C₁₂ alkyl, and mixtures thereof;each R¹ is independently hydrogen, a unit which can substitute forhydrogen selected from the group consisting of: i) —NHCOR³⁰; ii) —COR³⁰;iii) —COOR³⁰; iv) —COCH═CH₂; v) —C(═NH)NH₂; vi) —N(R³⁰)₂; vii) —NHC₆H₅;viii) —CON(R³⁰)₂; ix) —CONHNH₂; x) —NHCN; xi) —OCN; xii) —CN; xiii) F,Cl, Br, I, and mixtures thereof; xiv) —OR³⁰; xv) —NHCHO; xvi) —OH; xvii)—NHN(R³⁰)₂; xviii) —NHOR³⁰; xxiv) —CNO; xxv) —NCS; xxvi) —SO₃M; xxvii)—OSO₃M; xxviii) —SCN; xxix) —P(O)H₂; xxx) —PO₂; xxxi) —P(O)(OH)₂; xxxii)—SO₂NH₂; xxxiii) —SO₂R³⁰; xxxiv) —NO₂; xxxv) —CF₃, —CCl₃, —CBr₃; xxxvi)and mixtures thereof, or a C₁-C₁₂ substituted or unsubstitutedhydrocarbyl unit; each R² is independently hydrogen, a C₁-C₁₂substituted or unsubstituted hydrocarbyl unit, and mixtures thereof; Xis —OH or —NHR¹².
 2. A conjugate according to claim 1 wherein R has theformula:

wherein R⁶ is selected from the group consisting of hydrogen and methyl.3. A conjugate according to claim 1 wherein R has the formula:

wherein R⁶ is selected from the group consisting of hydrogen and methyl;each R⁷ is independently hydrogen, methyl or —C(O)OR⁹, and mixturesthereof; R⁹ is hydrogen, C₁-C₁₂ alkyl, and mixtures thereof.
 4. Aconjugate according to claim 1 having the formula:


5. A conjugate according to claim 1 having the formula:


6. A photo-labile pro-fragrance conjugate delivery system comprising: A)from about 0.001% by weight, of a photo-activated pro-fragranceconjugate according to claim 1; and B) the balance carriers and adjunctingredients.
 7. A laundry detergent comprising: A) from about 0.001% byweight, of a photo-activated pro-fragrance conjugate according to claim1; B) from about 10% by weight, of a detersive surfactant; and C) thebalance carriers and adjunct ingredients.
 8. A perfume or fine fragrancecomprising: A) from about 0.001% by weight, of a photo-activatedpro-fragrance conjugate according to claim 1; B) from about 0.01% toabout 99% by weight, of an admixture of fragrance raw materials; and C)the balance carriers and adjunct ingredients.
 9. A hair shampoo orconditioner comprising: A) from about 0.001% by weight, of aphoto-activated pro-fragrance conjugate according to claim 1; B) fromabout 0.01% to about 5% by weight, of an admixture of fragrance rawmaterials; and C) the balance carriers and adjunct ingredients.